“眼镜”状碘化亚铜配合物的调光和双光子发光性质

doi:10.7503/cjcu20190657

高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (4): 646.doi: 10.7503/cjcu20190657

• 庆祝《高等学校化学学报》复刊40周年专栏 • 上一篇下一篇

“眼镜”状碘化亚铜配合物的调光和双光子发光性质

尹少云^1,²,张露尹^1,³,王政¹,潘梅^1,^*()

^1. 中山大学化学学院, 广州 510275
^2. 广东工业大学分析测试中心, 广州 510006
^3. 兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室, 材料科学与工程学院, 兰州 730050

收稿日期:2019-12-11 出版日期:2020-04-10 发布日期:2020-02-17
通讯作者: 潘梅 E-mail:panm@mail.sysu.edu.cn
基金资助:
国家自然科学基金资助(21771197, 21821003)

Glass-like Cuprous Iodide Complexes with Photoluminescence Tuning and Two-photon Emission Properties ^†

YIN Shaoyun^1,²,ZHANG Luyin^1,³,WANG Zheng¹,PAN Mei^1,^*()

^1. School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China
^2. Analysis and Test Center, Guangdong University of Technology, Guangzhou 510006, China
^3. State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, China

Received:2019-12-11 Online:2020-04-10 Published:2020-02-17
Contact: Mei PAN E-mail:panm@mail.sysu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(21771197, 21821003)

摘要/Abstract

摘要：

将半柔性的π-不饱和双吡啶端基配体3-pebtd与CuI分别在不同的溶剂中分层扩散, 经自组装得到8种具有Cu₂I₂L₂构型的眼镜状碘化亚铜配合物. 利用X射线单晶衍射、 X射线粉末衍射和元素分析等方法确定了配合物的结构. 对配合物的光物理性质进行了表征, 结果表明, 不同溶剂中自组装得到的配合物的单光子发光均表现出单一荧光峰, 这可归因于卤素到配体的电荷转移( ³XLCT); 并且这些配合物的发光颜色由492 到518 nm可调, 量子产率为33.1%~68.5%. 同时, 这类配合物表现出较优异的双光子发光性质, 有望将其用于生物成像领域.

关键词: 碘化亚铜配合物, 调光, 双光子发光, 双吡啶端基配体

Abstract:

Eight kinds of glass-like cuprous iodide complexes with Cu₂I₂L₂ configurations were self-assembled from CuI with semi-flexible 3-pebtd ligand with unsaturated π-backbone and bipodal pyridine terminals in different solvents. The complexes were characterized by X-ray single crystal diffraction, X-ray powder diffraction, elemental analysis, and so on. The photophysical properties of the complexes were studied, and the results show that the one-photon emissions of the complexes obtained in different solvents show single fluorescence bands assigning to the halogen to ligand charge transfer( ³XLCT). The luminescent colors of the complexes were adjustable from 492 to 518 nm, and the quantum yield was 33.1%~68.5%. At the same time, these complexes exhibit excellent two-photon emission properties and are expected to be used in the field of biological imaging.

Key words: Cuprous iodide complex, Photoluminescence tuning, Two-photon emission, Bipodal pyridine terminal ligand

中图分类号:

O641

TrendMD:

尹少云, 张露尹, 王政, 潘梅. “眼镜”状碘化亚铜配合物的调光和双光子发光性质. 高等学校化学学报, 2020, 41(4): 646.

YIN Shaoyun, ZHANG Luyin, WANG Zheng, PAN Mei. Glass-like Cuprous Iodide Complexes with Photoluminescence Tuning and Two-photon Emission Properties ^†. Chem. J. Chinese Universities, 2020, 41(4): 646.

图/表 7

Scheme 1 Synthetic route of 3-pebtd ligand

Fig.1 Perspective drawing of the crystal structure of Cu-DCM H atoms and solvents are omitted for clarity.

Fig.2 Excitation(a, b) and emission(c) spectra of 3-pebtd in solid statea. λex=290 nm; b. λex=394 nm; c. λem=250 nm.

Fig.3 Excitation(A) and emission(B) spectra of Cu2I2L2, emission photos under 254 nm lamp(C), temperature-dependent photoluminescence spectra(D) of Cu-TCM

Table 1 Lifetime, PLQY and Cu—Cu bond distance of Cu2I2L2 complexes

Complex	λ_max/nm	Lifetime/μs	PLQY(%)	d_Cu—Cu/nm
Cu-TCM	518	7.16	58.1	0.27608(16)
Cu-Isopropanol	512	7.62	55.6	0.27673(12)
Cu-MeCN	510	7.83	65.9	0.27654(10)
Cu-EA	510	8.02	33.1	0.27072(11)
Cu-MeOH	506	8.04	60.5	0.27547(11)
Cu-EtOH	506	8.18	68.4	0.27178(11)
Cu-Aceton	499	6.82	54.8	0.27120(14)
Cu-DCM	492	7.85	68.5	0.26873(15)

Table 2 Temperature-dependent lifetime of Cu-TCM

Temperature/K	300	200	150	100	77
Lifetime/μs, τ_{518 nm}	7.16	12.71	13.23	13.43	13.22

Fig.4 Power-dependent emission spectra of Cu-TCM(λex=812 nm)(A), lg(PL intensity)-lg(Power) relationship(B), change in slope of emission intensity for threshold determination(C) and TPA cross sections from 740 to 960 nm(D)Inset of (A): emission photo of Cu-TCM under 812 nm femtosecond-laser which is the same color as under 254 nm lamp.

参考文献 18

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“眼镜”状碘化亚铜配合物的调光和双光子发光性质

Glass-like Cuprous Iodide Complexes with Photoluminescence Tuning and Two-photon Emission Properties ^†

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“眼镜”状碘化亚铜配合物的调光和双光子发光性质

Glass-like Cuprous Iodide Complexes with Photoluminescence Tuning and Two-photon Emission Properties †

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Glass-like Cuprous Iodide Complexes with Photoluminescence Tuning and Two-photon Emission Properties ^†